Detergent composition



Aug. 9, 1966 J. T. INAMORATO DETERGENT COMPOSITION Filed Oct. l, 1963INVENTOR. JAcK THoMAs INAMoRATo 3,265,624 DETERGENT COMPGSE'HON IlackThemas lnamorato, Flushing, NSY., assigner to Colgate-PairnoiiveCompany, New York, NX., a corporation of Delaware Fiied st. 1, i963,Ser. No. 312,968 i@ Claims. (Cl. 252-9?) This invention relates todetergent compositions, and more particularly to anionic detergentcompositions containing a chlorine bleach, such -compositions beingcharacterized -by controlled foam levels and particularly effectiveheavy duty cleansing power at use concentrations as hereinafterdescribed.

The development of a universally acceptable heawy duty laundrycomposition satisfactory `for use in any washing machine has beencomplicated by the housewifes acceptance of laundering machines havingdifferent mechanical characteristics.V At present, mechanicalcharacteristics determine to a large extent the nature of a detergentproduct that may satisfactorily be used in a particular machine. Forexample, highly eiective heavy duty detergent products containinganionic detergents may be satisfactorily used in top-'loading machinesin which agitation of the Wash solution is provided by a reciprocatingagitator or a pulsating agitator mounted in a vertical position. Suchproducts produce. a high stable `foam which persists throughout thelaundering cycle. However, this same high stable foam tends to interferewith use of such products at concentration levels consistent withsatisfactory detergency in front-loading washing machines in whichagitation is provided by a horizontally mounted rotating drum havinginternal ridges thereon. It has been found that high foam levels in thelatter type machines adversely affect detergency action by impedingagitation of the soiled laundry such that the laundered articles stilleibit high residual soil levels. This foam also increases mechanicalwear which, in turn, leads to higher maintenance costs, Further, eX-cessive foam levels often cause a front-loading machine to foam over,resulting in puddles of detergent solution in the oor area around themachine which must be mopped up by the housewife or laundry operator.Thus, this type of machine has created a need for controlled sudsingdetergents.

In attempting to solve the problem of excessive foam levels, detergentcompositions containing nonionic synthetic detergents have beendeveloped. Such compositions are based on alkylene oxide condensationproducts and these condensates generally possess cleansing ability witha minimum of suds. However, indications are that in the laundering ofnormally soiled clothes such co-mpositions are not equal in cleansingaction to the high sudsing anionic detergents and possess the addeddisadvantage of being incompatible with chlorine bleaches which aredesirable constituents of modern-day, heavyduty detergent compositions.

Therefore, a further need exists for controlled sudsing detergentcompositions containing particularly effective anionic detergentmateria-ls in combination with chlorine bleaches. Such desiredcompositions wlould provide superior detergency and would truly beuniversally acceptable for use in all laundering machines, e.g.,agitator-type and tumbler-type washing machines.

It is also known in the art that certain cationic agents are useful indetergent compositions, particularly to rende-r textiles soft. However,such cationic agents generally react with anionic detergents to formprecipitates which are deposited upon articles being washed, therebygiving the washed articles an undesirable appearance. This reaction orinteraction has eifectively depleted the 3,265,624 Patented August 9,1966 concentration of an anionic detergent in a washing bath to thedetriment of detergency action and, therefore,

should be avoided.

It is an object of the present invention, therefore, to provide adetergent composition of controlled sudsing capability. Another objectis to provide a controlled sudsing composition containing an effectiveanionic detergent and a chlorine bleach compatible therewith. A furtherobject is to provide an association of a cationic agent and a chlorinebleach, such association effectively controlling sudsing capabalities ofan anionic detergent composition without materially decreasing thecleansing action of the composition. Another object is to provide a sudsdepressing additive composition. Still another object is to provide acontrolled sudsing, heavy-duty detergent composition. A further objectis to provide a composition of the last-mentioned character suitable foruse in laundering machines of diverse types. Other objects o-f theinvention will become apparent from the following description.

Broadly stated, according to the present invention the foregoing objectsare realized with compositions comprising:

(a) a quaternary ammonium salt having one higher alkyl group andpreferably a quaternary ammonium salt represented by the general formulawherein R1 is a higher alkyl group containing fromv and (b) an organicchlorine-containing bleach such as a heterocyclic N-ch'lor imide oralkali metal salt thereof.

Another embodiment of the invention comprises cornpositions (a) and (b),each identified above, and a water-soluble, builder salt.

Another embodiment of the invention serving to meet the foregoingobjects comprises compositions comprising:

(a) and (b), each identified above,

(c) a Iwater-soluble Ianionic organic detergent, and

(d) a water-soluble, builder salt.

In general, compositions of the invention are eminently satisfactory foruse in any of the present day automatic washing machines because theyare characterized by particularly effective detergency, effectivebleaching action at normal washing temperatures and a moderate sudsinglevel in tumbler-type Washing machines operating on normally soiledlaundry.

One component, (a), of the compositions of this invention is a cationicmaterial, namely, a quaternary arnmonium compound having the generalformula:

wherein R1 is a higher alkyl group containing from about l0 to about 20carbon atoms, R2 and R3 are lower alkyl groups each having from 1 to 3carbon atoms, and R4 is selected from the group consisting of loweralkyl groups having from l to 3 carbon atoms and aralkyl groups, and Xis a halogen. Such compounds are characterized by some solubility inwater. A wide variety of suitable cationic sulface active agents can beemployed herein, typical of which are:

Stearyl dimethyl benzyl ammonium chloride,

Cetyl trimethyl ammonium bromide,

Lauryl trimethyl ammonium chloride,

Lauryl dimethyl benzyl ammonium chloride,

Myristyl diethyl benzyl ammonium bromide,

Decyl trimethyl ammonium bromide,

Arachidyl diethyl benzyl ammonium chloride,

Oleyl triethyl ammonium chloride,

n-Alkyl dimethyl ethyl benzyl ammonium chloride wherein the n-alkylcomprises a mixture of normal C12 to C18 groups.

It is to be understood that mixtures of two or more cationic agents canbe employed if desired.

Suitable qu-aternary ammonium compounds are available as 95 percentactive powders, 57 percent active aqueous pastes and in 25-50 percentaqueous alcholic solutions. It is preferred to use the 95 percent activepowder material, but choice of physical form is dependent upon storageand production facilities.

Component (b) of the compositions of this invention is a water-soluble,organic chlorine-containing dry bleach, particularly a heterocyclicN-chloro imide or alkali metal salt thereof. Such cyclic imides havefrom 4 to about 6 members in the ring, and are characterized by thefollowing structure:

o o1 o ll I Il -C-N-C- in which the electron donating nitrogen is doublyactivated to a highly acidic state by virtue of its proximity to twoelectro-positive carbonyl groups. Such N-chloro imides are known to thepri-or art, usually being prepared by passing chlorine gas into analkaline aqueous solution of the parent imide. Compounds suitable foruse in the present compositions include the N-chloro derivatives ofcyanuric acid (eg. mono, diand tri-chloro-cyanuric acid) and hydantoinas well as N-chloro succinimide, N-chloro malonimide, N-chlorophthalimide and N-chloro napthalimide. In general it is preferred toemploy those imides containing a plurarity of chlorine-containingnitrogen atoms, e.g. trichlorocyanuric acid, dichlorocyanuric acid,sodium and potassium dichloroisocy-anurates, etc. Suitable N-chlorohydant-oins include: 1,3-dichloro- 5,5-dimethyl hydantoin;N-monochloro-C,Cdimethy1 hydantoin; methylene-bis-(N-chloro-C,Cdimethy1hydantoin); l,3,-dichloro-S-methyl-S-isobutyl hydantoin; 1,3-dichloro-S-methyl-S-ethyl hydantoin; 1,3-dichloro-5,5di isobutylhydantoin; 1,3-dichloro-S-methyl-S-n-amyl hydantoin, and the like.

Such bleaches are compatible with anionic-detergentcontainingcompositions contemplated herein. They are effective at normal Washingtemperatures. Normally, the bleaching agents are employed in aproportion in the mixture such that about 2O to about 200 parts permillion (ppm.) of available chlorine will be present in a washing bath.However, other proportions of the bleach can be used if desired.

- One bleach or a mixture of the same identified as component (b), canbe used herein. Additional dry bleaching -agents can also be present inthe new compositions. Typical of the additional bleaching agents aresodium hypochlorite (NaOCl-5H2O), sodium and potassium perborates,potassium monopersulfate, etc.

As indicated above, one component of compositions contemplated herein isa water-soluble, anionic, organic detergent (c) above. Such a detergentis stable in the presence of the bleaching agent (b). It is to beunderstood that one or several of such detergents can be used incompositions of this invention. The said detergents may be designated aswater-soluble salts of organic reaction products having in theirmolecular structure an anionic solubilizing group such as SO4H, SO3H,COOH and PO4H and an alkyl or aralkyl radical having about 8 to 22carbon atoms in the alkyl group. Suitable detergents are anionicdetergent salts having alkyl substituents of 8 to 22 carbon atoms, suchas: Water-soluble higher fatty acid alkali metal soaps, e.g., sodiummyristate and sodium palmitate; water-soluble sulfated and sulfonatedanionic alkali metal and alkaline earth metal detergent salts containinga hydrophobic higher alkyl moiety, such as salts of higher alkyl monoorpoly-nuclear aryl sulfonates having from about 8 to 18 carbon atoms inthe alkyl group which may have a straight or branched srtucture, e.g.,sodium dodecylbenzene sulfonate, magnesium tridecylbenzene sulfonate,lithium or potassium pentapropylene benzene sulfonate; -alkali metalsalts of sulfated condensation products of ethylene oxide (e.g. 3 to 20and preferably 3-10 mols of ethylene oxide per mol of other compound)with aliphatic alcohols containing 8 to 18 carbon atoms, or with alkylphenols having alkyl groups containing 6 to 18 carbon atoms, eg., sodiumnonyl phenol pentaethoxamer sulfate and sodium lauryl alcoholtriethoxamer sulfate; alkali metal salts of sulfated alcohols containingfrom about 8 to 18 carbon atoms, e.g., sodium lauryl sulfate and sodiumstearyl sulfate; alkali metal salts of higher fatty acid esters of lowmolecular weight alkylol ysulfonic acid, eg., fatty acid esters of thesodium salt of isethionic acid; fatty ethanolamide sulfates; fatty acidamides of amino alkyl sulfonic acids, eg., lauric acid amide of taurine;alkali metal salts of hydroxy alkane sulfonic acids having 8 to 18carbon atoms in the alkyl group, e.g., hexadecyl alpha-hydroxy sodiumsulfonate. In general these organic surface active agents are employedin the form of their alkali metal salts or alkaline earth metal saltsbecause such salts possess the requisite stability, water solubility,and low cost essential to practical utility.

It is preferred to use a combination of detergents, specifically one ormore water-soluble, anionic, non-soap organic detergents with one ormore water-soluble, higher fatty acid salt detergents. The twodetergents and the quatemary compound cooperate to provide anaccelerated rate of collapse of static foam without adversely affectingeither dynamic foam balance or the detersive efciency of a composition.

Another component of compositions of this invention is a water-soluble,builder salt, component (d). The salt can be inorganic or organic,illustrative of which are:

Trisodium phosphate,

Tetrasodium pyrophosphate,

Sodium acid pyrophosphate,

Sodium tripolyphosphate,

Sodium monobasic phosphate,

Sodium dibasic phosphate,

Sodium hexametaphosphate,

Sodium metasilicate,

Sodium silicates, Na2O/SiO2 of 1.6/1 to 3.2/1, Sodium carbonate,

Sodium sulfate,

Borax,

Nitriloacetic acid trisodium salt,

Ethylene diamine tetraacetic acid tetrasodium salt, etc.

Mixtures of two or more inorganic or organic salts can be used, as canmixtures of inorganic organic salts.

Particularly preferred herein are water-soluble, alkali metalpolyphosphate builder salts. These salts form water-soluble complexeswith calcium and magnesium ions found in hard water and thereby preventthe formation of insoluble salts which tend to deposit upon textilesduring a Washing cycle. Further, such phosphates enhance the detersiveefficiency of anionic detergents, aid in controlling sudsing power andaid in keeping soil suspended in the washing bath after its removal fromthe soiled textiles.

Proportions of the various components of the new compositions should beproperly related in order to achieve the desired objects. The weightratio of a quaternary ammonium salt to a chlorine-containing bleach,(a)/(b), should range from about 0.01/1 to about 2/1, preferably from0.1/l to 1/1. As a general guiding principle, proportions of components(a) and (b) of this foam depressing combination generally vary inverselywith each other. Thus, a minor proportion of cationic agent (a) issufficient when the proportion of chlorine bleach (b) is high, and alarger proportion of cationic agent (a) is required when a lesser amountof chlorine bleach (b) is used generally. In addition, the nature of thecationic agent (a) used and the proportions of the anionic detergent (c)and builder (d) affect the proportion of cationic agent to be used.r[herefore, the cationic agent (a) is to be suitably proportioned ineach composition such that ardesired suds level can be attained.

Advantageous additive compositions for depressing foam are thosecomprising from about l to about 67 percent by weight of one or more ofthe quaternary ammonium salts having one higher alkyl group and fromabout 33 to about 99 percent by weight of one or more of the bleaches.Such compositions generally comprise amounts of from about 2 to about 30percent by weight of heavy-duty detergent compositions.

As indicated, a quantity of the bleach employed should be such thatabout to about 200 p.p.m. of available bleach is present in a washingbath having a total detergent concentration greater than about 0.075percent by weight, and preferably from about 0.1 to about 0.4 percent byweight. With respect to an anionic organic detergent (c), from about 5to about 50 percent by weight of a detergent composition should comprisethis component. Preferably, the quantity will be of the order of about7.5 to 40 percent by weight. In general, for laundering compositions,the balance of a formulation is primarily a water-soluble, builder saltor salts. The latter is generally used in an amount ranging from about 5to about 90 percent by weight, particularly the polyphosphate, andpreferably from about percent to `about 60 percent. In such launderingcompositions, the amounts of quaternary compound and bleach will bevariable as indicated above. Generally, the quaternary compound will bepresent in amounts from about 0.01 to about 4, and preferably from about0.3 to about 3, percent by weight. The bleach will be present in anamount ranging from about 2 to about 30, and preferably from about 5 toabout 20, percent by weight.

In addition to the foregoing components, the compositions contemplatedherein can beneficially include various other substances generallyemployed in the art in such detergent compositions, provided that theuse of any such materials does not substantially adversely affect thedesired properties of the compositions. Examples of suitable materialsare hydrotropic solubilizing agents such as sodium xylene and toluenesulfonates; sodium carboxymethylcellulose and polyvinyl alcoholanti-redeposition agents; optical or uorescent brightener materials ofthe triazole or benzidine sulfone type which are partieularly effectivein the presence of a chlorine-containing bleach; germicides; coloringagents; perfumes; and the like.

Preferred compositions advantageously contain a hydrophobic cellulosicsoil-suspending agent which is soluble or dispersible in water also. Thejoint use of the combination of the cellulosic compound and polyvinylalcohol is particularly effective for soil-suspending properties duringthe washing of a variety of fabrics, including both cotton and syntheticfibers such as nylon, dacron and resin-treated cottons. The mixture isused preferably in a total amount of 0.1 to 2 percent by weight of thesolids. Preferred cellulosic compounds are the alkali metal salts of acarboxy lower alkyl cellulose having carbons in the alkyl group, such asthe sodium Suitable salts are sodium carboxyethylcellulose, thecellulose sulfates and lower alkyl and hydroxyalkylcellulose ethers suchas methylethyland hydroxyethyl-celluose.

The compositions of this invention are stable during storage. Thesecompositions can be prepared by dry blending the powder or granularmaterials in any suitable blender. Preferably all the ingredients,except the bleaching agent, are prepared in particulate form by heatdrying an aqueous slurry, such as by spray drying or drum drying attemperatures about 212 F., and the dry bleach is then blended with theheat dried composition.

In the manufacture of an additive composition comprising a cationicagent and a bleach, the two materials can be intimately admixed indesired proportions in a ribbon blender -or similar mixing apparatus.Manufacture of the low-sudsing, heavy duty detergents can beaccomplished by following various procedures used for compoundingdetergent compositions. However, a preferred procedure involves additionof Water to a soap crutcher, followed by an aqueous solution of ananionic detergent (e.g., a sulfonate) and then by a builder or builders(eg, sodium tripolyphosphate). Thereafter, a cationic agent is added.The temperature of the slurry formed in the crutcher is maintained atabout i60-189 F. for a period of time ranging from about 10 minutes toone hour. A smooth, pumpable mixture having a total solids content ofabout 55-60 percent by weight, is formed. The mixture is then pumpedinto a spray tower where it is spray-dried with air heated to about 600F., whereupon a product in the form of beads is obtained. A bleach isthen admixed with the product in bead lor in any other suitable form ina suitable mixer such as a twin-shell blender, ribbon blender, etc.

A particularly advantageous process herein involves forming a fluidaqueous slurry comprising water and an anionic organic detergent with afatty acid salt. The slurry flows or is pumped into a conventional soapcrutcher or any other suitable mixinfy apparatus such as a ribbonblender. The anionic detergent should desirably be added to the crutcherprior to addition of the quaternary compound in order to avoid formationof any significant amount of insoluble, anionic-cationic complex. Theother ingredients are then added in any suitable order and form. Thecationic quaternary ammonium compound is added, usually as a fine whitepowder, with stirring. The resulting slurry should be sufficiently fluidat the elevated temperatures to insure adequate mixing and formation ofa uniform product, and is subjected to a heat treatment at an elevatedtemperature such as within the range of about to about 200 F., andusually from about to 155 F. The slurry is heated by external means oreven by the exothermic heat of reaction of certain ingredients. Forexample, the addition of hydratable inorganic salts such as theanhydrous forms of sodium tripolyphosphate and sodium pyrophosphateresults in exothermic reactions as hydration occurs. It is desirablegenerally to add the polyphosphate and/or other builder salt or salts inthe final stages of the crutching operation. A fatty acid salt can beadded at `any suitable stage of the crutching operation, preferablybefore addition of polyphosphate. Thus, all of the components, exceptthe bleach and miscellaneous characterizing agents, can be added tothecrutcher without any need to shield one component from another.Mixing time is suicient to insure adequate mixing and will usually be atleast a few minutes, e.g. 5 minutes. The aqueous mixture prior to dryingcan be aged at the elevated temperature for a time sufficient to insureadequate solubilization or hydration of certain ingredients. Such agingperiod can be a number of hours, such as up to about 8 hours. Ingeneral, it is preferred to employ time intervals of less than threehours and preferably less than one hour. It is understood thatexcessively high temperatures or unduly long aging periods are to beavoided to prevent any possible decomposition and insure efcientprocessing.

The solids content of the aqueous slurry is usually within the range offrom about 20 percent to 90 percent of total solids. In the manufactureof heat-dried products involving vaporization of the water, the solidscontent is usually within the range of about 40 to 65 percent by weight,the remainder being substantially free Water content. The slurry isusually maintained at a ternperature from about 160 to 180 F. Thisslurry is subjected to known spray-drying operations utilizingtemperatures above about 212 F. to produce the detergent composition inparticulate form, generally in the form of hollow, thin-walled sphericalparticles. The `detergent composition can be transformed into beads,granules, flakes, chips, powders or the like as desired by use of theconventional techniques.

In spray-drying the aqueous slurry, it is atomized or forced throughspray nozzles into towers, with small liquid particles discharged fromthe nozzles becoming solidified and drying as they contact or fallthrough a stream or vortex of heated air or other inert gas which is atabout 600 F. The composition is produced thereby in the form of hollowthin-walled spheres or beads having a small residual moisture contentusually of about 3 to l5 percent by weight.

The present invention is more fully described and exempliiied in thefollowing examples. It is to be understood, however, that the inventionis not to be limited to any specific form of materials or conditions setforth in the examples, but is limited solely by the description in thespecification and the appended claims. All quantities are expressed inparts by weight unless otherwise indicated.

Example 1 In this illustration, a comparison is made of several relatedcompositions one of which is typical of the new compositionscontemplated herein. All parts are by weight unless otherwise specified.The compositions cornpared are:

(A) Comprising essentially 12 percent of sodium tridecylbenzenesulfonate (anionic detergent), 3 percent sodium tallow soap (anionicdetergent), 50 percent sodium tripolyphosphate (builder), 24 percentsodium sulfate (builder), and 11 percent water;

(B) Composition A in which l percent of the Water is replaced with 1percent stearyl dimethyl benzyl ammonium chloride (cationic agent);

(C) Composition A in which percent of the water is replaced with 10percent of potassium dichloroisocyanurate (bleach); and

(D) Composition A in which 11 percent of the waterall of the water-isreplaced by 1 percent of stearyl dimethyl benzyl ammonium chloride andby 10 percent of potassium dichloroisocyanurate (identied herein asProduct 1).

Composition A was formed by mixing an aqueous solution of the sulfonatewith an aqueous solution of the soap. Dry builders were added to andwere mixed with the resulting aqueous solution. The concentration of theentire detergent system (sulfonate, soap and builders) was approximately0.15 percent by weight. Composition B was formed in much the samemanner, except that an aqueous solution of the cationic agent was mixedwith the aqueous solutions containing sulfonate and soap prior toaddition of the builders. Composition C was formed by adding the drybleach to a composition formed in accordance with the procedure forpreparing Composition B. `Composition D was prepared by: mixing togetheraqueous solutions containing, respectively: sulfonate, -soap andcationic agent; adding dry builders to the resulting solution; and thenadding the dry bleach to the solution formed following addition of thebuilders.

Compositions A through D were subjected to an evaluation test, referredto as a Dynamic Foam Test, which has been found to correlate withconditions normally encountered with use of detergent compositions. Foambehavior of the compositions is determined in the presence of soil byemploying soiled cotton fabrics in a standard laboratory Tergotometerapparatus. The soil employed was a synthetic sebum comprising:

Percent wt. Palmitic acid 10 Stearic acid 5 Oleic acid 15 Coconut oil 20Olive oil 20 Squalene 5 Parafnn (M. Pt., 48 C.) 10 Spermaceti 15 Thetest procedure used follows:

(1) 50 grams of the sebum mixture was dissolved in a 1:1isopropanol-benzene mixture, and was made up to 250 milliliters in avolumetric flask (1 ml.=200 milligrams of sebum);

(2) 0.2 ml. of the solution formed in 1 was added to each of a number ofterry cloth swatches measuring 1 inch by 1 inch;

(3) 0.45 gram of the composition to be tested, and 300 milliliters ofwater at 125 F., were added to a beaker and were thoroughly mixed;

(4) The mixture formed in 3 was tested in the Tergotometer for a periodof 3 minutes, and the height of the foam which formed was recorded assoon as the Tergotometer stopped;

(5 One soiled terry cloth swatch was added to the beaker and step 4 wasrepeated;

(6) 1 soiled swatch was added at 3 minute intervals until foam hadcompletely collapsed.

Results of the test so conducted are provided in the figure appendedhereto wherein a series of curves are shown. Foam height, in inches, isplotted as the ordinate, and the cumulative amount of sebum soil addedis plotted as the abscissa, Curves identified by A, B, C, and D areobtained by testing Compositions A through D, respectively. The curvelabelled E represents the calculated or expected foam behavior ofComposition D, based upon the properties of the individual components.

A number of features are shown by the curves set out in the figure,namely:

1) Composition A exhibits excellent foam stability in the presence ofsoil, but would be unacceptable for use in tumbler-type automaticwashers unless unrealistically heavy soil levels were encountered;

.(2) Composition B indicates that the addition of `a minor amount (1%)of a cationic agent to Composition A depresses the dynamic foam in thepresence of soil;

(3) Composition C exhibits such foam stability in the presence of soilas to be undesirable for use in tumblertype automatic washers despitethe fact that addition of the bleaching agent to Composition A reducesthe dynamic foam stability in the presence of soil, though not enough toeliminate a foaming problem at normal soil levels corresponding to -150mgs. of sebum soil in tumbler-type automatic washers;

(4) Composition D contains both the 1% cationic quaternary ammoniumcompound of Composition B and the bleaching agent of Composition C andexhibits the absence of foam in the 100-150 mgs. soil range which isequivalent to soil range expected for normal loads of soiled fabrics intumbler-type washing machines; this curve illustrates that by suitablyadjusting the proportions of the two components-cationic compound andbleacha product having a predetermined foam level in tumblertype washingmachines can be formulated; and

(5) Comparison of the curve for Composition D with curve E, representingthe calculated or expected foam behavior for Composition D, reveals asubstantial synergistic foam depressant relationship.

Example 2 Components: Parts Sodium tridecyl benzene sulfonate 25Potassium dichloroisocyanurate (equivalent to 100 p.p.m./17 gallons ofwater) 10 Stearyl dimethyl benzyl ammonium chloride 3 Sodiumtripolyphosphate 25 Sodium sulfate 29 The composition of ExampleZ-identied herein as product 2-was prepared in the same manner as wasComposition D of Example 1. It was tested at 0.15% concentration in theDynamic Foam Test, wherein the foam level fell from 11/2 inches withoutany soil to 1/2 inch after the addition of 80 mgs. of soil and to atrace level after 160 mgs. of sebum soil. For comparison, in the absenceof the chlorine bleach-cationic agent foam depressant combination, thefoam level Vremained at 11/2 inches until 500 mgs. of sebum soil hadbeen added. Approximately one inch of foam was formed in a tumble-r4washer when laundering a normally soiled eight pound load of soiledtextiles with product 2.

The compositions shown in Examples 3 through 18, below, were prepared byfollowing the procedure of Example 1, Composition D.

Examples 3 and 4 Parts Components Sodium tridccyl benzene sulionatc 9 9Potassium dichloroisocyanurate 2 5 Stearyl dimethyl benzyl ammoniumchloride.. 0.8 0.5 Sodium tripolyphosphate 30 30 Sodium sulfate 51 48The compositions of Examples 3 and 4 were tested at 0.15 concentrationin the Dynamic Foam Test and the foam level fell from l inch in theabsence of soil to a trace level after 40 mgs. were added. Bothcompositions are satisfactory for laundering soiled textiles intumblertype washing machines.

Examples 5 and 6 Parts Components High titer soda talloW soap 12 l2Potassium dichloroisocyanm-ate 2 Stearyl dimethyl benzyl ammoniumchloride 0.3 Sodium tripolyphosphate 50 50 Sodium sulfate 30 27 Theproduct 5 of Example 5 was evaluated in the Dynamic Foam Test at 0.15concentration and exhibited the following foam behavior: mg. soil-1%inches; 40 mgs. soil- 1% inches; 80 mgs. soil-1% inches; 120 mgs.soil-7A; inch; 160 mgs. soil-V2 inch. The effect of incorporating thefoam control combination of the invention is characterized by theproduct 6 of Example 6 which exhibits an initial foam height of /fs inchand a trace foam level in the presence of 80 mgs. of sebum soil. Thecompositions also demonstrate the foam suppressing ellect of theadditive mixture of this invention.

v Examples 7, 8 and 9 Parts Components Sodium tridecyl benzene sulfonate12 12 12 High titer soda tallow soap 3 3 3 Potassiumdicliloroisocyanurate 10 10 Dodecyltrimethyl ammonium chloride 0.8 1. 53.0 Sodium tripolyphosphate 50 50 50 Sodium sulfate 16 l5 14 Examples 10and 11 The following compositions showed excellent heavy dutyperformance with low sudsing characteristics and served as excellentdetergents for use in tumblentype washers.

Parts Components Sodium tridecyl benzene sulfonatc 6. 0 Sodium laurylalcohol suliato G. 0 12. 0 High titer soda tallow soap 3.0 3. 0 Sodiumtripolyphosphate 50.0 50.0 Mixed 0124315 alkyl dimethyl benzyl ammoniumchloride 0.8 0. 8 Sodium carboxy-methyl cellnlose 0.5 0.5 Potassiumdichloroisocyanurate... 10.0 10.0 Water 8. 5 8. 5 Sodium sulfate 15.215. 2

Example 12 The following composition was prepared: Components: PartsSodium tridecyl benzene sulfonate 12.0 High titer soda tallow soap 3.0Sodium tripolyphosphate 50.0 Stearyl dimethyl benzyl ammonium chloride0.8 Trichloro cyanuric acid 10.0 Water 1.5 Sodium sulfate 22.7 Thiscomposition gave the same general results as Example 2 and provedsatisfactory for use in horizontal, front-loading washers.

Examples 73, 14 and 15 Parts Components Sodium alpha-hydroxy liexadecylsulfonate l2 Sodium lauryl alcohol sulfate 12 Sodium sulfate oftctraethoxylated nonyl phenol l5 co (/15) soap 3. 2 2 3.5 Stearyldimethyl benzyl ammonium ohloride 1. 2 0.8 1 Sodium silicate solids 3 33 Sodium tripolypliosph 40 45 40 Sodium sulfate. 25.6 22. 2 22.5Potassium dichlorc ate 10 10 10 Water 5 5 5 The -term coco refers tofatty acid groups found in coconut 4oil fatty acids. Such acids containfrom about 8 to about 18 carbon atoms per molecule, predominating lIlC12-C14 aCldS.

Examples 16, 17 and J8 Parts Components Sodium tridecyl benzenesulfonate 12 l2 12 Sodium tallow soap 3 3 3 Nitriloacetic acid,trisodium salt 50 5 Ethylene diamine tetraacetic acid, tetr sodium salt5 Sodium sulfate 30 30 Sodium tripolyphosphate 35 35 Sodium silicate 3 33 Stearyl dimethyl benzyl ammonium chor 0.8 1 1 Potassiumdichloroisocyanurate 10 10 10 Water q.s. q.s. q.s.

1 1 Example 19 Components: Parts Sodium tridecyl benzene sulfonate 12High titer soda tallow soap 3.2 Stearyl dimethyl benzyl ammoniumchloride 0.8 Sodium tripolyphosphate 50 Sodium silicate solids 3 Sodiumsulfate 16.9 Sodium carboxymethyl cellulose 0.5 Polyvinyl alcohol 0.2Brighteners, perfume, etc. 0.4 Potassium dichloroisocyanurate Water 3The product 19 of this example has been found to exhibit highly superiorproperties as a heavy-duty detergent composition. Product 19 was formedin accordance with the spray drying techniques described above.

The foregoing compositions performed satisfactorily when used intumbler-type Washing machines.

In summary, compositions of the present invention provide detergentcompositions acceptable for use in both agitator-type and tumbler-typewashing machines. Further, these compositions exhibit eiectivedetergency action of anionic detergent phosphate mixtures, bleachingaction of a chlorine bleach and desired foam control in the presence ofsoil. Foam control is achieved by a novel combination of a cationicagent and the chlorine bleaching agent.

Performance of the compositions of this invention is excellent.Advantages realized therewith include: soft, uffy towels, diapers, etc.;smooth, silky sheets, pillow cases, etc.; easy-to-iron shirts, sheets,etc.; reduced cling on nylon and other synthetics; long garment life,less wrinkling.

The new compositions can be used to launder a variety of fabrics, whichcan be made from natural animal bers, natural vegetable fibers, mineralfibers and synthetic bers. These include wool, silk, cotton, linen,glass, acetate, rayon, nylon, Orlon, Dacron, and others. The fabrics canbe those classied as outer garments, under garments, diapers, etc.

It is to be understood, in keeping with the illustrations given above,that the additive compositions, etc. of this invention can be in solidform in the character of freeilowing powders, granules, tablets, etc. Bythe term solids used herein, it is intended to include sizes and shapesof material having at least one dimension of relatvely low order, suchas grains, chips, ilakes and other forms having proportionally largesurface areas, and in any other suitable form The new compositions canbe packaged in paper, plastic or any other suitable packaging medium.For example, an additive combination of a cationic `agent and a bleachcan be packaged in a Water-soluble plastic material such as polyvinylalcohol, for use either in a wash or a rinse cycle, or in both cycles,or in loose particulate from such as powders and granules. If desired,the bleach can also be contained in a Water-soluble polyvinyl alcoholpacket or the like and the other ingredients can be combined in thecontainer which also includes the bleach packet. Anther technique forinsuring long shelf life involves coating of the bleach with a coatingagent such as a suitable fatty alcohol, e.g. stearyl alcohol; the coatedbleaching agent can then be mixed with all other ingredients withoutnecessity for separated compartments in a container.

Although the present invention has been described and illustrated with areference to specic examples, it is understood that modifications andvariations of composition and procedure may be made by those skilled inthe art within the principle and scope of the invention as expressed inthe appended claims.

I claim:

1. A controlled sudsing, heavy-duty detergent composition consistingessentially of:

(a) from about 5 to about 50 percent by weight of -a water-soluble,anionic organic detergent having an alkyl group of about 8 to 22 lcarbonatoms in its molecular structure,

(b) from about 5 to about 90 percent by weight of a builder saltselected from the group consisting of sodium inorganic phosphates,silicates, carbonates, sulf-ates, borates and mixtures thereof,

(c) from about 0.01 to about 4 percent by weight of a quaternaryammonium salt having |the formula wherein R1 is an alkyl group of about10 to 2Q carbon atoms, R2 and R3 are alkyl g-r-oups of 1 to 3 carbonatoms each, R4 is selected from the group consisting of alkyl groups 'ofl to 3 carbon atoms and benzyl groups, and X is a halogen selected fromthe group consisting of chlorine and bromine, and (d) from about 2 Itoabout 30 percent by 4weight of a heterocyclic N-chloro imide bleachcontaining a plurality of chlorine-containing nitrogen atoms, the totalquantity of (c) and (d) being sufficient to depress foam normallydeveloped in the absence of said (c) and (d) to a pre-determined levelat use concentrations of said composition under laundering conditions.

2. A controlled sud'sing, heavy-duty detergent composition consistingessentially of:

(a) from about 5 to about 50 percent by Weight of a water-soluble,alkali metal anionic organic detergent having an alkyl group of about 8to 22 carbon atoms in its molecular structure, (b) from about 5 to about90 percent by weight of a builder salt selected from the groupconsisting of sodium inorganic phosphates, silicates, carbonates,sulfates, borates and mixtures thereof, (c) from about 0.01 to about 4percent by weight of a quarternary ammonium salt having the formulawherein R1 is an alkyl group of about l0' to 20 carbon atoms, R2 and R3are alkyl groups of l to 3 carbon atoms each, R4 is selected from thegroup consisting of `alkyl groups of l to 3 carbon atoms and benzylgroups, land X isa halogen selected lfrom the group consisting ofchlorine and bromine, and

(d) from about 2 to about 30 percent by weight of a bleach selected fromthe group consisting of t-richlorocyanuric acid, dischlorocyanuric acid,sodium dichloroisocyanurate and potassium dichloroisocyanurate.

3. A composition dened by claim 2 wherein the total quantity of (c)|(d)is sufcient to provide from about 20 to about 200 parts pe-r lmillion ofavailable chlorine in a washing bath at total detergent compositionconcentrations in excess of 0.075 percent by weight in said bath.

4. A composition defined by claim 2 wherein the total quantity of(c)-|(d) lis sucient to provide from about 20 to about 200 parts permillion of available chlorine in a Washing bath at total detergentcomposition concentrations from about 0.1 to about 0.4 percent by weightin said bath.

5. A composition defined by claim 2 wherein said builder salt is aWater-soluble, alkali metal inorganic phosphate.

6. A composition -delined by claim 2 wherein the ratio tof (c)/(d) isfrom about 0.01/1 to about 2/1.

7. A controlled sudsing, heavy-duty detergent composition consistingessentially of:

(a) from about 7.5 to about 40 percent by weight of a water-soluble,anionic organic detergent selected from the group consisting of alkalimetal sulfates, sulfonates and carboxylates having in their molecularstructure :an alkyl group `of about 8 to 22 carbon atoms,

(b) from about 25 t=o about 60 percent by weight of a water-soluble,alkali metal inorganic phosphate builder salt, and

(c) from about 2 to about 30 percent by weight of a mixture containingfrom about 1 to about 67 percent by weight of a quaternary ammonium salthaving the formula wherein R1 is an alkyl group of about 10 to 20 carbonatoms, R2 and R3 are alkyl groups of 1 to 3 carbon atoms each, R4 isselected from the group consisting of -alkyl groups of 1 to 3 carbonatoms and benzyl groups, and X is a halogen selected from the groupconsisting of chlorine and bromine, and from about 33 to about 99percent by weight of a bleach selected from `the group consisting oftrichlorocyanuric acid, dichlorocyanuric acid, sodiumdichloroisocyanurate and potassium dischloroisocyanurate.

8. A detergent composition consisting essentially of about .01-4% of aquaternary ammonium salt represented by the formula [Ra-IlI-Rd X whereinR1 is an alkyl group of about 10 to 20 carbon atoms, R2 and R3 are alkylgroups of l to 3 carbon atoms each, R4 is selected from the groupconsisting of alkyl groups of 1 to 3 carbon atoms and benzyl groups, andX is a halogen selected from the group consisting of chlorine andbromine, about 2-30% of a bleach selected from the group consisting ofdichlorocyanuric acid, trichlorocyanuric acid, sodiumdichloroisocyanurate and potassium dichloroisocyanurate, the ratio ofsaid quaternary arnmonium compound to said bleach material being from`about .01/ 1 to about 2/1 by weight, 5-50% of watersoluble, alkalimetal, anionic organic detergent having an alkyl group of about 8 to 22carbon atoms and about to 90% of a water-soluble alkali metal inorganicphosphate, said amounts being by weight thereof.

9. A detergent composition consisting essentially of about 5 to 50% byweight of a water-soluble anionic organic detergent selected from thegroup consisting of alkali metal sulfates, sulfonates and carboxylateshaving an alkyl group of about 8 to 22 carbon atoms in their molecularstructure, about 5 to 90% by weight of a Water-soluble alkali metalinorganic phosphate builder salt and about 2 to 30% by weight of amixture of (a) a. quaternary ammonium salt Irepresented by the formulawherein R1 is an alkyl group of about 10 to 2O carbon atoms, R2 and R3are alkyl -groups of 1 to 3 carbon atoms each, R4 is selected from thegroup consisting of alkyl groups of l to 3 carbon atoms and benzylgroups, and X is a halogen selected from the group consisting ofchlorine and bromine and (b) a bleach selected from the group consistingof -dichlorocyanuric acid, trichlonocyanuric acid, sodiumdichloroisocyanurate an potassium dichloroisocyanurate, the Weightratito of said quaternary ammonium compound to said bleach being fromabout 0.01/l lto about 2/1.

10. A detergent composition in dry, granular form consisting essentiallyof about 5 to 50% by weight of an alkali metal higher alkyl benzenesulfonate detergent having about 8 to 18 carbons in the alkyl group,about 5 to 90% by weight of a water-soluble alkali metal inorganicphosphate, about 0.01 to 4% by weight of stearyl dimethyl benzylammonium chloride, and about 2 to 30% by weight of an alkali metal saltof dichlonocyanuric :acid selected from the group consisting of sodiumand potassium salts.

References Cited by the Examiner UNITED STATES PATENTS 2,834,737 5/1958Farkas 252-98 2,929,816 3/1960 Chamberlain 252-102 XR 2,987,435 6/1961Davies et al. 252--187 XR 2,988,471 6/1961 Fuchs et al 252-186 XR3,044,962 7/ 1962 Brunt et al 252--106 XR FOREIGN PATENTS 525,648 5/1956Canada.

OTHER REFERENCES Monsanto ACL, Technical Bulletin, 1-177, January 1960,Monsanto Chemical Co., St. Louis, Missouri, pages 3, 10, 11.

ALBERT T. MEYERS, Primary Examiner.

J ULIUS GREENWALD, Examiner.

M. WEINBLATT, Assistant Examiner.

7. A CONTROLLED SUDSING, HEAVY-DUTY DETERGENT COMPOSITION CONSISTINGESSENTIALLY OF: (A) FROM ABOUT 7.5 TO ABOUT 40 PERCENT BY WEIGHT OF AWATER-SOLUBLE, ANIONIC ORGANIC DETERGENT SELECTED FROM THE GROUPCONSISTING OF ALKALI METAL SULFATES, SULFONATES AND CARBOXYKATES HAVINGIN THEIR MOLECULAR STRUCTURE AN ALKYL GROUP OF ABOUT 8 TO 22 CARBONATOMS, (B) FROM ABOUT 25 TO ABOUT 60 PERCENT BY WEIGHT OF AWATER-SOLUBLE, ALKALI METAL INORGAIC PHOSPHATE BUILDER SALT, AND (C)FROM ABOUT 2 TO ABOUT 30 PERCENT BY WEIGHT OF A MIXTURE CONTAINING FROMABOUT 1 TO ABOUT 67 PERCENT BY WEIGHT OF A QUATERNARY AMMONIUM SALTHAVING THE FORMULA